Patent GB-553269-A (GB)
Title: Improvements in and relating to the manufacture of sulphonamido compounds
Filed: 1941-04-29
Abstract: 553,269. Sulphenamido and sulphonamido compounds. MANCHESTER OXIDE CO., Ltd., BANN, B., KRUG, P., WHEELER, D. E., TAYLOR, W., and GLADDING, G. April 29. 1941, Nos. 5527/41, 12575/41 and 7078/42, Samples furnished. [Class 2 (iii)] Benzenesulphonamide and its p-substituted derivatives are prepared by oxidation of the corresponding benzenesulphenamides, e.g. by means of alkali or alkaline earth metal permanganate or hypochlorite. The substituent in the p-position is preferably a halogen atom or a nitrogen-containing group, such as acylamino or nitro, and after the oxidation treatment, the substituent may be converted into the amino group by reaction with ammonia, hydrolysis or reduction ; the sulphenamide may also be substiuted in the amide group, e.g. by an alkyl or aryl group. The starting materials may be obtained by first converting a diphenyldisulphide, obtainable from the thiocyanobenzenes whose preparation is described in Specifications 513,473 and 514,203, by treatment with caustic alkali, into the corresponding benzenesulphenyl chloride by chlorinating in a non-aqueous medium, and then reacting with ammonia, a cylic imine or a primary or secondary amine ; they may also be prepared by interaction of a benzenesulphenic acid ester with an amine or by treatment of a benzenesulphenamide with a primary amine. According to the examples, (1) diphenyldisulphide is chlorinated in chloroform, the resulting benzenesulphenyl chloride treated with diethylamine, and the product oxidized with potassium permanganate to benzenesulphondiethylamide ; 4:4<SP>1</SP>-dimethyldiphenyldisulphide is similarly treated to give p-toluenesulphondiethylamide ; (2) 4:4<SP>1</SP>-dinitrodiphenyldisulphide is chlorinated, treated with n-butylamine and oxidised with potassium permanganate to produce p-nitrobenzenesulphon - n - butylamide; (3) 2 - (p - nitrobenzenesulphonamido) - quinoline is prepared by reacting p-nitrobenzenesulphenyl chloride with 2-aminoquinoline and oxidising as above ; (4) p-aminobenzenesulphonamide is formed when p-nitrobenzenesulphenamide is oxidised with potassium permanganate and reduced with iron and hydrochloric acid ; (5) p-nitrobenzenesulphenyl chloride is reacted with diethylamine, the sulphendiethylamide oxidised with potassium or calcium permanganate in aqueous solution, and the product reduced with stannous chloride to yield paminobenzenesulphondiethylamide ; ' (6) pnitrobenzenesulphonanilide is prepared by reacting p-nitrobenzenesulphenyl chloride with aniline and oxidising the product with potassium permanganate ; (7) 4:4<SP>1</SP>-dichlordiphenyldi - sulphide is chlorinated in chloroform to pchlorbenzenesulphenyl chloride, which is then treated with sodium ethoxide to form the ethyl ester of p-chlorbenzenesulphenic acid; on reacting the latter with piperidine and oxidising the product with potassium permanganate, pchlorbenzenesulphonylpiperidine is obtained ; the chlorine atom may be replaced by the amino group by use of ammonia ; (8) p-chlorbenzenesulphondiethylamide is prepared by oxidising with potassium permanganate the reaction product of p-chlorbenzenesulphenyl chloride and diethylamine ; (9) 4:41-diacetyldiaminodiphenyldisulphide is treated in chloroform solution with chlorine at a temperature below 0‹C., the product reacted with diethylamine to form p-acetylaminobenzenesulphendiethylamide, which is then oxidized with potassium permanganate and finally hydrolyzed, yielding p-aminobenzenesulphondiethylamide. Reference is made to a product containing an isoquinolyl substituent in the amido group, but those containing pyridyl, guanyl, pyrimidyl and thiazolyl substituents are disclaimed. Specification 379,683 also is referred to. The samples furnished under Sect. 2 (5) consist of (1) p-chlorbenzenesulphonanilide prepared by chlorinating 4:4<SP>1</SP>-dichlordiphenyldisulphide, reacting the resulting p-chlorbenzenesulphenyl chloride with sodium ethoxide to give p-chlorbenzenesulphenyl ethyl ester, which is treated with aniline and oxidized with potassium permanganate ; (2) p-chlorbenzenesulphondiethylamide formed by oxidizing with potassium permanganate the reaction product of p-chlorbenzenesulphenyl ethyl ester and diethylamine ; (3) benzenesulphonanilide obtained by chlorinating diphenyldisulphide and treating with sodium ethoxide, reacting the resulting benzenesulphenethyl ester with aniline and oxidizing with potassium permanganate ; (4) benzenesulphondiethylamide prepared by oxidizing with potassium permanganate the reaction product of benzenesulphenethyl ester with diethylamine ; (5) p-nitrobenzenesulphonanilide produced by chlorinating 4:41- dinitrodiphenyldisulphide, treating with sodium ethoxide to form the sulphenyl ester, reacting the latter with aniline and oxidizing the product with potassium permanganate; (6) p-nitrobenzenesulphonbutylamide prepared by oxidizing with potassium permanganate the reaction product of p-nitrobenzenesulphenyl ethyl ester and n-butylamine; (7) p-acetylaminobenzenesulphonanilide obtained by reacting p-acetylaminobenzenesulphenyl chloride with aniline and oxidizing the product with potassium permanganate ; (8) p-nitrobenzenesulphonanilide prepared by heating p-nitrobenzenesulphenamide with aniline and oxidizing the p-nitrobenzenesulphenanilide so formed with potassium permanganate.